Functionalized silicate nanoparticle composition, removing and exfoliating asphaltenes with same

ABSTRACT

Removing an asphaltene particle from a substrate includes contacting a silicate nanoparticle with a chemical group to form a functionalized silicate nanoparticle, the chemical group includes a first portion; and a second portion comprising a nonaromatic moiety, the first portion being bonded to the silicate nanoparticle; contacting the asphaltene particle with the functionalized silicate nanoparticle, the asphaltene particle being disposed on the substrate; interposing the functionalized silicate nanoparticle between the asphaltene particle and the substrate; and separating the asphaltene particle from the substrate with the functionalized silicate nanoparticle to remove the asphaltene particle. A composition includes a functionalized silicate nanoparticle comprising a reaction product of a silicate nanoparticle and a functionalization compound; and a fluid. The functionalization compound includes a chemical group that includes a first portion, the first portion being directly bonded to the silicate nanoparticle in the functionalized silicate nanoparticle; and a second portion including an aromatic moiety or a nonaromatic moiety.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 14/659,919filed Mar. 17, 2015, which is a continuation-in-part of U.S.Nonprovisional patent application Ser. No. 13/731,232, filed Dec. 31,2012, the disclosures of both applications being incorporated byreference in their entirety herein.

BACKGROUND

Asphaltenes are a major component in crude oil, and there is generalagreement as to the deleterious effects of asphaltenes in the reductionof oil extraction and processing in the petrochemical industry.Asphaltenes can deposit in the pores of formations, blocking the flow offluids. Additionally, asphaltenes can precipitate from a stream of oiland coat boreholes, production tubing, and transport lines. Moreover, ina processing facility, asphaltenes can foul processing equipment andpoison catalysts.

Asphaltene molecules have been widely reported as having a fusedpolyaromatic ring system and containing heteroatoms such as sulfur,oxygen, nitrogen, and the like. The heteroatoms may be part of thearomatic ring system or part of other carbocyclic rings, linking groups,or functional groups. Two structural motifs for asphaltene molecules arethe so-called continental and archipelago structures. In the continentalstructure, alkyl chains connect to and branch from a centralpolyaromatic ring system, which is believed to contain several fusedaromatic rings, e.g., 5 or more aromatic rings. In the archipelagostructure, multiple polyaromatic ring systems are connected by alkylchains that may contain a heteroatom, and additional alkyl chains extendfreely from the polyaromatic rings. The number of fused aromatic ringsin the continental structure can be greater than the number of fusedaromatic rings in the archipelago structure.

In addition to the aromatic regions of the asphaltenes, heteroatomsprovide the asphaltenes with polar regions, and the terminal alkylchains provide hydrophobic regions. Consequently, it is believed thatasphaltene molecules aggregate into various micellular structures inoil, with the alkyl chains interacting with the aliphatic oilcomponents. Resin from the oil can insert between aromatic planes ofneighboring asphaltene molecules in asphaltene aggregates, aiding inmaintaining their micellular structure. Asphaltenes can precipitate fromoil in structures where asphaltene molecules form stacked layers havingaligned aromatic regions and aligned aliphatic regions.

Materials and methods for treating and removal of asphaltenes from oilenvironments such as a reservoir would be well received in the art.

BRIEF DESCRIPTION

The above and other deficiencies of the prior art are overcome by, in anembodiment, a process for removing an asphaltene particle from asubstrate, the process comprising: contacting a silicate nanoparticlewith a chemical group to form a functionalized silicate nanoparticle,the chemical group comprising: a first portion; and a second portioncomprising a nonaromatic moiety, the first portion being directly bondedto the silicate nanoparticle in the functionalized silicatenanoparticle; contacting the asphaltene particle with the functionalizedsilicate nanoparticle, the asphaltene particle being disposed on thesubstrate; interposing the functionalized silicate nanoparticle betweenthe asphaltene particle and the substrate; and separating the asphalteneparticle from the substrate with the functionalized silicatenanoparticle to remove the asphaltene particle from the substrate.

In another embodiment, a composition comprises: a functionalizedsilicate nanoparticle comprising a reaction product of a silicatenanoparticle; and a functionalization compound comprising quaternaryammonium salt, quaternary phosphonium salt, alkoxy silane, halide,guanidine, guanidinium salt, biguanidine, biguanidinium salt, sulfoniumsalt, or a combination thereof and a fluid, wherein thefunctionalization compound includes a chemical group comprising: a firstportion, the first portion being directly bonded to the silicatenanoparticle in the functionalized silicate nanoparticle; and a secondportion comprising: an aromatic moiety or a nonaromatic moiety, and thecomposition is effective to remove an aromatic compound from a substratecomprising a metal, composite, sand, rock, mineral, glass, formation,downhole element, or a combination thereof.

A process for removing an asphaltene particle from a substratecomprises: contacting a silicate nanoparticle with a chemical group toform a functionalized silicate nanoparticle, the chemical groupcomprising: a first portion; and a second portion comprising anonaromatic moiety, the first portion being directly bonded to thesilicate nanoparticle in the functionalized silicate nanoparticle; andthe second portion comprising a moiety of a guanidine, a guanidiniumsalt, a biguanidine, a biguanidinium salt, or a sulfonium salt;contacting the asphaltene particle with the functionalized silicatenanoparticle, the asphaltene particle being disposed on the substrate;interposing the functionalized silicate nanoparticle between theasphaltene particle and the substrate; and separating the asphalteneparticle from the substrate with the functionalized silicatenanoparticle to remove the asphaltene particle from the substrate.

DETAILED DESCRIPTION

A detailed description of one or more embodiments is presented herein byway of exemplification and not limitation.

An asphaltene particle includes any collection of asphaltene molecules,for example, a micelle, precipitate, layered asphaltene molecules,aggregate, cluster, and the like. Interactions among the asphaltenemolecules in an asphaltene particle can include hydrogen bonding,dipole-dipole interactions, and π-π interactions. Without wishing to bebound by theory, disruption of these interactions can lead toexfoliation of an asphaltene molecule from the asphaltene particle.Since asphaltenes form layered aggregates that resemble the layeredsheet structure of graphite, perturbing the layered asphaltene structureallows for asphaltene production from decomposed, e.g., exfoliatedasphaltene aggregates. Such deagglomeration is useful for extraction ofoil from an oil environment, e.g., a formation, as well as forrestoration of the permeability of a plugged or flow-constrictedreservoir. The methods and compositions herein are applicable to amultitude of environments such as downhole as well as to a groundenvironment.

It has been found that perturbing the internal structure of asphalteneparticles, for example, in a micelle or other aggregate, can lead toincreased quality of oil containing asphaltenes. Further, degradation ofasphaltene aggregates herein enhances production of petroleum fluid in adownhole, subsurface, or ground environment. Furthermore, removal ofasphaltene from pores of a rock formation, within a reservoir, or from asidewall of a tubular, production tubing, borehole, or transportationtube can improve the permeability of such structures, leading toincreased quality of oil as well as enhanced oil recovery from, e.g., areservoir.

Moreover, without wishing to be bound by theory, it is believed thatheteroatoms in the asphaltene structure interact strongly with variousmaterials such as metals, minerals, and polar surfaces. Therefore,asphaltenes coat rock formations, sand, metal, and polymer componentssuch as tubulars, sand screens, or packers. These deleterious adhesionslead to equipment malfunction, failure, or flow blockage. In order toalleviate this issue, a composition herein can separate and remove theasphaltene particles that interact, such as by adsorption or blockage,with such items or materials.

In an embodiment, a composition includes a functionalized silicatenanoparticle and a fluid. The functionalized silicate nanoparticle is areaction product of a silicate nanoparticle and a functionalizationcompound. The functionalization compound includes a chemical group thathas a first portion, e.g., a linker, and a second portion (e.g., atail), which includes an aromatic or a nonaromatic moiety. The firstportion is directly bonded to the silicate nanoparticle in thefunctionalized silicate nanoparticle. The composition is effective toremove an aromatic or olefin compound, e.g., an asphaltene, from asubstrate. The substrate can be a metal, composite, sand, rock, mineral,glass, formation, downhole element, or a combination thereof.

As used herein, the term “aromatic” includes an aryl or heteroarylgroup. Thus, an aromatic compound includes an aryl moiety or heteroarylmoiety.

The functionalization compound can have a structure of formula 1,formula 2, formula 3, formula 4 or a salt thereof, formula 5 or a saltthereof, formula 6 or a salt thereof, or formula 7:

wherein

a is an integer from 1 to 4;

b is an integer from 0 to 3;

the sum of a and b is 4 (i.e., a+b=4) so that the valence of A and Si iscompletely filled and not exceeded

m is 0 or 1, n is independently an integer from 0 to 20;

Ar is an aromatic moiety or a nonaromatic moiety, wherein each Ar is thesame or different, and when Ar is an aromatic moiety, Ar isindependently a C6 to C30 aryl group, C3 to C30 heteroaryl, orcombination thereof;

L is a linker group, wherein each L is the same or different, and L isindependently a bond, C1 to C30 alkylene, C3 to C30 cycloalkenylene, C1to C30 fluoroalkylene, C3 to C30 cycloalkylene, C3 to C30heterocycloalkylene, C6 to C30 arylene, C6 to C40 aralkylene, C6 to C30aryleneoxy, C3 to C30 heteroarylene, C6 to C40 heteroaralkylene, C2 toC30 alkenylene, C2 to C30 alkynylene, C1 to C30 amide, amine, C1 to C30oxyalkylene, C1 to C30 oxyarylene, oxygen (O), sulfur (S), or acombination thereof. L can be substituted or unsubstituted (with theexception of O and S). Moreover, L can be linear or branched, with theexception of O and S.

A is nitrogen (N) or phosphorous (P);

X⁻ is an anion of a halogen;

R¹ is a substituent on A or Si, wherein each R¹ is the same ordifferent, and R¹ independently is hydrogen, C1 to C30 alkyl group, C1to C30 alkenyl group, C1 to C30 alkoxy group, C1 to C30 alkynyl group,C1 to C30 aryloxy, halogen, C6 to C30 aryl group, C1 to C30 amide,amino, C3-C30 cycloalkenyl, C3-C30 cycloalkyl, C3-C30 fluoroalkyl,C1-C30 heteroalkyl, C3-C30 heteroaryl, hydroxy, C1-C30 oxyalkyl, or acombination thereof, and each foregoing group can be substituted orunsubstituted or can be linear or branched;

R₁-R₉ and R₁₁-R₂₄ are independently hydrogen atom, alkyl, heterocyclic,carbonyl, amino, amide, sulfonamide, phosphoramide, imide moiety, anaromatic moiety, or a combination thereof;

R₁₀ is a bond, alkylene, heterocyclic biradical, carbonyl, amino, amide,sulfonamide, phosphoramide, imide biradical, an aromatic moiety, or acombination thereof;

R₂₅ is a halogen or an alkoxy group; and

G is of formulas (4)-(7), wherein at least one of R₁-R₉ and R₁₁-R₂₄ is adivalent group attached to oxygen atom or silicon atom.

As used herein, “alkenyl” refers to a straight or branched chain,monovalent C2-C10 hydrocarbon group having at least one carbon-carbondouble bond (e.g., ethenyl (—HC═CH₂)). As used herein, “alkenylene”refers to a straight or branched chain, divalent C2-C30 hydrocarbongroup having at least one carbon-carbon double bond (e.g., ethenylene(—HC═CH—)). As used herein, “alkoxy” refers to an alkyl group that islinked via an oxygen (i.e., —O-alkyl). Non-limiting examples of C1 toC30 alkoxy groups include methoxy groups, ethoxy groups, propoxy groups,isobutyloxy groups, sec-butyloxy groups, pentyloxy groups, iso-amyloxygroups, and hexyloxy groups.

As used herein, “alkyl” refers to a straight or branched chain saturatedaliphatic hydrocarbon having the specified number of carbon atoms,specifically 1 to 12 carbon atoms, more specifically 1 to 6 carbonatoms. Alkyl groups include, for example, groups having from 1 to 50carbon atoms (C1 to C50 alkyl).

As used herein, “alkylene” refers to a straight, branched or cyclicdivalent aliphatic hydrocarbon group, and can have from 1 to about 18carbon atoms, more specifically 2 to about 12 carbons. Exemplaryalkylene groups include methylene (—CH₂—), ethylene (—CH₂CH₂—),propylene (—(CH₂)₃—), cyclohexylene (—C₆H₁₀—), ethyleneoxy (—CH₂CH₂O—),methylenedioxy (—O—CH₂—O—), or ethylenedioxy (—O—(CH₂)₂—O—).

As used herein, “alkynyl” refers to a straight or branched chain,monovalent hydrocarbon group having at least one carbon-carbon triplebond (e.g., ethynyl). As used herein, “alkynylene” refers to a straightor branched chain divalent aliphatic hydrocarbon that has one or moreunsaturated carbon-carbon bonds, at least one of which is a triple bond(e.g., ethynylene). As used herein, “amide” refers to a group of theformula C(O)—N(Rx)(Ry) or —N—C(O)—Rx, wherein Rx is an alkyl, analkenyl, an alkynyl, a cycloalkyl, an aryl group, or heteroaryl group;and Ry is hydrogen or any of the groups listed for Rx. As used herein,“C1 to C15 amine group” is a group of the formula —N(Rw)(Rz), wherein Rwis a C1 to C15 alkyl, a C1 to C15 alkenyl, a C1 to C15 alkynyl, a C3 toC15 cycloalkyl, a C6 to C15 aryl, or C3 to C15 heteroaryl group; and Rzis hydrogen or any of the groups listed for Rw.

As used herein, “aryl” refers to a cyclic moiety in which all ringmembers are carbon and at least one ring is aromatic, the moiety havingthe specified number of carbon atoms, specifically 6 to 24 carbon atoms,more specifically 6 to 12 carbon atoms. More than one ring may bepresent, and any additional rings may be independently aromatic,saturated or partially unsaturated, and may be fused, pendant,spirocyclic or a combination thereof.

As used herein, “arylalkylene” group is an aryl group linked via analkylene moiety. The specified number of carbon atoms (e.g., C7 to C30)refers to the total number of carbon atoms present in both the aryl andthe alkylene moieties. Representative arylalkyl groups include, forexample, benzyl groups.

As used herein, “arylene” refers to a divalent radical formed by theremoval of two hydrogen atoms from one or more rings of an aromatichydrocarbon, wherein the hydrogen atoms may be removed from the same ordifferent rings (preferably different rings), each of which rings may bearomatic or nonaromatic. As used herein, “aryloxy” refers to an arylmoiety that is linked via an oxygen (i.e., —O-aryl). As used herein,“cycloalkenyl” refers to a monovalent group having one or more rings andone or more carbon-carbon double bond in the ring, wherein all ringmembers are carbon (e.g., cyclopentyl and cyclohexyl).

As used herein, “cycloalkyl” refers to a group that comprises one ormore saturated and/or partially saturated rings in which all ringmembers are carbon, such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, adamantyl and partially saturatedvariants of the foregoing, such as cycloalkenyl groups (e.g.,cyclohexenyl) or cycloalkynyl groups. Cycloalkyl groups do not includean aromatic ring or a heterocyclic ring. When the numbers of carbonatoms is specified (e.g., C3 to C15 cycloalkyl), the number refers tothe number of ring members present in the one or more rings.

As used herein, “cycloalkenylene” refers to a stable aliphatic5-15-membered monocyclic or polycyclic, divalent radical having at leastone carbon-carbon double bond, which comprises one or more ringsconnected or bridged together. Unless mentioned otherwise, thecycloalkenylene radical can be linked at any desired carbon atomprovided that a stable structure is obtained. If the cycloalkenyleneradical is substituted, this may be so at any desired carbon atom, onceagain provided that a stable structure is obtained. Examples thereof arecyclopentenylene, cyclohexenylene, cycloheptenylene, cyclooctenylene,cyclononenylene, cyclodecenylene, norbornenylene, 2-methylcyclopentenylene, 2-methylcyclooctenylene.

As used herein, “cycloalkylene” refers to a divalent radical formed bythe removal of two hydrogen atoms from one or more rings of a cycloalkylgroup (a nonaromatic hydrocarbon that comprises at least one ring).

As used herein, “fluoroalkyl” refers to an alkyl group in which at leastone hydrogen is replaced with fluorine. “Fluoroalkylene” refers to analkylene group in which at least one hydrogen is replaced with fluorine.

As used herein, “halogen” refers to one of the elements of group 17 ofthe periodic table (e.g., fluorine, chlorine, bromine, iodine, andastatine).

As used herein, the prefix “hetero” means that the compound or groupincludes a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein theheteroatom(s) is each independently N, O, S, Si, or P.

As used herein, “heteroalkyl” group is an alkyl group that comprises atleast one heteroatom covalently bonded to one or more carbon atoms ofthe alkyl group. Each heteroatom is independently chosen from nitrogen(N), oxygen (O), sulfur (S), and phosphorus (P).

As used herein, “heteroaryl” refers to a monovalent carbocyclic ringgroup that includes one or more aromatic rings, in which at least onering member (e.g., one, two or three ring members) is a heteroatom. In aC3 to C30 heteroaryl, the total number of ring carbon atoms ranges from3 to 30, with remaining ring atoms being heteroatoms. Multiple rings, ifpresent, may be pendent, spiro or fused. The heteroatom(s) are generallyindependently selected from nitrogen (N), oxygen (O), phosphorus (P),and sulfur (S).

As used herein, “heteroarylene” refers to a divalent radical formed bythe removal of two hydrogen atoms from one or more rings of a heteroarylmoiety, wherein the hydrogen atoms may be removed from the same ordifferent rings (preferably the same ring), each of which rings may bearomatic or nonaromatic.

As used herein, “oxyalkyl” refers to an alkyl group to which at leastone oxygen atom is covalently attached (e.g., via a single bond, forminga hydroxyalkyl or ether group, or double bond, forming a ketone oraldehyde moiety). As used herein, “oxyalkylene” refers to a divalentradical comprising an alkylene group to which at least one oxygen atomis covalently attached (e.g., via a single bond, forming ahydroxyalkylene or an ether group, or double bond, forming a ketone oraldehyde moiety). As used herein, “oxyarylene” moiety is an aromaticgroup in which all ring members are independently chosen from carbon andoxygen.

As used herein, “substituted” means that the compound or group issubstituted with at least one (e.g., 1, 2, 3, or 4) substituentindependently selected from a hydroxyl (—OH), a C1-9 alkoxy, a C1-9haloalkoxy, an oxo (═O), a nitro (—NO₂), a cyano (—CN), an amino (—NH₂),an azido (—N₃), an amidino (—C(═NH)NH₂), a hydrazino (—NHNH₂), ahydrazono (—C(═NNH₂)—), a carbonyl (—C(═O)—), a carbamoyl group(—C(O)NH₂), a sulfonyl (—S(═O)₂—), a thiol (—SH), a thiocyano (—SCN), atosyl(CH₃C₆H₄SO₂—), a carboxylic acid (—C(═O)OH), a carboxylic C1 to C6alkyl ester (—C(═O)OR wherein R is a C1 to C6 alkyl group), a carboxylicacid salt (—C(═O)OM) wherein M is an organic or inorganic anion, asulfonic acid (—SO₃H₂), a sulfonic mono- or dibasic salt (—SO₃MH or—SO₃M₂ wherein M is an organic or inorganic anion), a phosphoric acid(—PO₃H₂), a phosphoric acid mono- or dibasic salt (—PO₃MH or —PO₃M₂wherein M is an organic or inorganic anion), a C1 to C12 alkyl, a C3 toC12 cycloalkyl, a C2 to C12 alkenyl, a C5 to C12 cycloalkenyl, a C2 toC12 alkynyl, a C6 to C12 aryl, a C7 to C13 arylalkylene, a C4 to C12heterocycloalkyl, and a C3 to C12 heteroaryl instead of hydrogen,provided that the substituted atom's normal valence is not exceeded.

The aromatic moiety of the functionalization compound can include anaryl group or heteroaryl group. Exemplary aryl groups include anthracyl,azulenyl, benzocyclooctenyl, benzocycloheptenyl, biphenylyl, chrysenyl,fluorenyl, indanyl, indenyl, naphthyl, pentalenyl, phenalenyl,phenanthrenyl, phenanthryl, phenyl, pyrenyl, tetrahydronaphthyl, aderivative thereof, or a combination thereof.

Exemplary heteroaryl groups include acridinyl, benzimidazolyl,benzofuranyl, benzofurazanyl, benzothiazolyl, benzothiophenyl,benzoxazolyl, carbazolyl. chromanyl, cinnolinyl, dibenzofuranyl,furazanyl, furopyridinyl, furyl, imidazolyl, indazolyl, indolinyl,indolizinyl, indolyl, isochromanyl, isoindolinyl, isoindolyl,isoquinolinyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl,oxazolyl, perimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl,phenoxathiinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl,purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl,pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl,thiadiazolyl, thiazolyl, thienyl, triazinyl, triazolyl, a derivativethereof, or a combination thereof. The heteroaryl group may be attachedat any heteroatom or carbon atom of the ring such that the result is astable structure. Thus, for example, pyridyl represents 2-, 3-, or4-pyridyl, thienyl represents 2- or 3-thienyl, and quinolinyl represents2-, 3-, or 4-quinolinyl, and the like.

According to an embodiment, a substituent of the aromatic moiety (e.g.,the aryl group or heteroaryl group) includes halogen, hydroxy, loweralkyl, lower alkoxy, lower aralkyl, —NR² ₂ (wherein R² is a loweralkyl), R³CONH (wherein R³ is phenyl or a lower alkyl), and —OC(O)R⁴(wherein R⁴ is hydrogen, alkyl, or aralkyl). Other substituents for thearomatic moiety can be —OR⁵, —OC(O)R⁵, —NR⁵R⁶, —SR⁵, —R⁵, —CN, —NO₂,—CO₂R⁵, —CONR⁵R⁶, —C(O)R⁵, —OC(O)NR⁵R⁶, —NR⁶C(O)R⁵, —NR⁶C(O)₂R⁵,—NR⁵—C(O)NR⁶R⁷, —NHC(NH₂)═NH, —NR⁵C(NH₂)═NH, —NHC(NH₂)═NR⁵, —S(O)R⁵,—S(O)₂R⁵, —S(O)₂NR⁵R⁶, —N₃, —CH(Ph)₂, perfluoro(C₁-C₄)alkoxy, andperfluoro(C₁-C₄)alkyl, in a number ranging from zero to the total numberof open valences on the aromatic moiety ring system; and where R⁵, R⁶,and R⁷ are independently selected from hydrogen, C1-C8 alkyl orheteroalkyl, unsubstituted aryl and heteroaryl, (unsubstitutedaryl)-(C1-C4)alkyl, (unsubstituted aryl)oxy-(C1-C4)alkyl, (unsubstitutedhetero aryl)-(C1-C4)alkyl, or (unsubstitutedheteroaryl)oxy-(C1-C4)alkyl.

In a specific embodiment, a substituent for the aromatic moiety of thearomatic compound includes, for example, an alkyl group (having 1 to 20carbon atoms, specifically 1 to 12 carbon atoms, and more specifically 1to 8 carbon atoms and including, e.g., methyl, ethyl, iso-propyl,tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl,cyclohexyl, and the like), an aryl group (having 6 to 30 nuclear carbonatoms, specifically 6 to 20 nuclear carbon atoms and including, forexample, phenyl, naphthyl, biphenylyl, anthranyl, phenanthryl, pyrenyl,chrysenyl, fluorenyl, and the like), an alkenyl group (having 2 to 20carbon atoms, specifically 2 to 12 carbon atoms, and more specifically 2to 8 carbon atoms and including, for example, vinyl, allyl, 2-butenyl,3-pentenyl, and the like), an alkynyl group (having 2 to 20 carbonatoms, specifically 2 to 12 carbon atoms, and more specifically 2 to 8carbon atoms and including, for example, propargyl, 3-pentynyl, and thelike), an amino group (having 0 to 20 carbon atoms, specifically 0 to 12carbon atoms, and more specifically 0 to 6 carbon atoms and including,for example, amino, methylamino, dimethylamino, diethylamino,diphenylamino, dibenzylamino, and the like), an alkoxy group (having 1to 20 carbon atoms, specifically 1 to 12 carbon atoms, and morespecifically 1 to 8 carbon atoms and including, for example, methoxy,ethoxy, butoxy, and the like), an aryloxy group (having 6 to 20 carbonatoms, specifically 6 to 16 carbon atoms, and more specifically 6 to 12carbon atoms and including, for example, phenyloxy, 2-naphthyloxy, andthe like), an acyl group (having 1 to 20 carbon atoms, specifically 1 to16 carbon atoms, and more specifically 1 to 12 carbon atoms andincluding, for example, acetyl, benzoyl, formyl, pivaloyl, and thelike), an alkoxycarbonyl group (having 2 to 20 carbon atoms,specifically 2 to 16 carbon atoms, and more specifically 2 to 12 carbonatoms and including, for example, methoxycarbonyl, ethoxycarbonyl, andthe like), an aryloxycarbonyl group (having 7 to 20 carbon atoms,specifically 7 to 16 carbon atoms, and more specifically 7 to 10 carbonatoms and including, for example, phenyloxycarbonyl and the like), anacyloxy group (having 2 to 20 carbon atoms, specifically 2 to 16 carbonatoms, and more specifically 2 to 10 carbon atoms and including, forexample, acetoxy, benzoyloxy, and the like), an acylamino group (having2 to 20 carbon atoms, specifically 2 to 16 carbon atoms, and morespecifically 2 to 10 carbon atoms and including, for example,acetylamino, benzoylamino, and the like), an alkoxycarbonylamino group(having 2 to 20 carbon atoms, specifically 2 to 16 carbon atoms, andmore specifically 2 to 12 carbon atoms and including, for example,methoxycarbonylamino and the like), an aryloxycarbonylamino group(having 7 to 20 carbon atoms, specifically 7 to 16 carbon atoms, andmore specifically 7 to 12 carbon atoms and including, for example,phenyloxycarbonylamino and the like), a sulfonylamino group (having 1 to20 carbon atoms, specifically 1 to 16 carbon atoms, and morespecifically 1 to 12 carbon atoms and including, for example,methanesulfonylamino, benzenesulfonylamino, and the like), a sulfamoylgroup (having 0 to 20 carbon atoms, specifically 0 to 16 carbon atomsand more specifically 0 to 12 carbon atoms and including, for example,sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and thelike), a carbamoyl group (having 1 to 20 carbon atoms, specifically 1 to16 carbon atoms and more specifically 1 to 12 carbon atoms andincluding, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl,phenylcarbamoyl, and the like), an alkylthio group (having 1 to 20carbon atoms, specifically 1 to 12 carbon atoms, and more specifically 1to 8 carbon atoms and including, for example, methylthio, ethylthio, andthe like), an arylthio group (having 6 to 20 carbon atoms, specifically6 to 16 carbon atoms, and more specifically 6 to 12 carbon atoms andincluding, for example, phenylthio and the like), a sulfonyl group(having 1 to 20 carbon atoms, specifically 1 to 16 carbon atoms and morespecifically 1 to 12 carbon atoms and including, for example, mesyl,tosyl, and the like), a sulfinyl group (having 1 to 20 carbon atoms,specifically 1 to 16 carbon atoms, and more specifically 1 to 12 carbonatoms and including, for example, methanesulfinyl, benzenesulfinyl, andthe like), a ureido group (having 1 to 20 carbon atoms, specifically 1to 16 carbon atoms, and more specifically 1 to 12 carbon atoms andincluding, for example, ureido, methylureido, phenylureido, and thelike), a phosphoramide group (having 1 to 20 carbon atoms, specifically1 to 16 carbon atoms, and more specifically 1 to 12 carbon atoms andincluding, for example, diethylphosphoramide, phenylphosphoramide, andthe like), a hydroxy group, a mercapto group, a halogen atom (forexample, a fluorine atom, chlorine atom, bromine atom, iodine atom, andthe like), a cyano group, a sulfo group, a carboxyl group, a nitrogroup, a hydroxamic acid, a sulfino group, a hydrazine group, an iminogroup, a heterocyclic group (having 1 to 30 carbon atoms, specifically 1to 12 carbon atoms, including, for example, a nitrogen atom, an oxygenatom and a sulfur atom as a heteroatom and including, for example,imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino,benzoxazolyl, benzimidazolyl, benzothiazolyl and carbazolyl), a silylgroup (having 3 to 40 carbon atoms, specifically 3 to 30 carbon atoms,and more specifically 3 to 24 carbon atoms and including, for example,trimethylsilyl, triphenylsilyl, and the like), and the like.

In an embodiment, the R group of formula (1), (2), or (3) is one of thepreceding substituents mentioned with the respect to the aromaticmoiety.

In an embodiment, the linking groups of formula (1), (2), or (3) includegroups obtained by converting the preceding substituents mentioned abovewith the respect to the aromatic moiety into divalent groups. Exemplarylinking groups are a hetero atom, a substituted or unsubstitutedalkylene group having 1 to 6 carbon atoms, a substituted orunsubstituted cycloalkylene group having 3 to 30 carbon atoms, asubstituted or unsubstituted arylene group having 6 to 30 nuclear carbonatoms, or a substituted or unsubstituted heteroarylene group having 5 to30 nuclear carbon atoms. The heteroatom can be, for example, an oxygenatom, a sulfur atom, a nitrogen atom and a silicon atom. The alkylenegroup can be, for example, methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, dimethylmethylene,diphenylmethylene, and the like. The cycloalkylene group can be, forexample, cyclopropylene, cyclobutylene, cyclopentylene andcyclohexylene, 1,1-cyclohexylene, and the like. The arylene group canbe, for example, phenylene, biphenylene, terphenylene, naphthylene,anthracenylene, phenathrylene, chrysenylene, pyrenylene, fluorenylene,2,6-diphenylnaphthalene-4′,4″-ene, 2-phenylnaphthalene-2,4′-ene,fluorenylene, and the like. The heteroarylene group can be, for example,a divalent residue of imidazole, benzimidazole, pyrrole, furan,thiophene, benzothiophene, oxadiazoline, indoline, carbazole, pyridine,quinoline, isoquinoline, benzoquinone, pyrrolidine, imidazolidine,piperidine, pyridylene, and the like.

According to an embodiment, the functionalization compound can be aquaternary ammonium salt, quaternary phosphonium salt, alkoxy silane,halide, a guanidine, a guanidinium salt, a biguanidine, a biguanidiniumsalt, a sulfonium salt, or the like.

Non-limiting examples of the aryl quaternary ammonium salt includebenzylammonium chloride, benzyldimethyldecylammonium chloride,benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammoniumchloride, benzyldimethylhexylammonium chloride,benzyldimethyl(2-hydroxyethyl)ammonium chloride,benzyldimethyl(2-hydroxymethyl) ammonium chloride,benzyldimethyloctylammonium chloride, benzyldimethylstearylammoniumchloride monohydrate, benzyldimethyltetradecylammonium chloride,benzyldodecyldimethylammonium bromide, benzyltributylammonium bromide,benzyltributylammonium chloride, benzyltributylammonium iodide,benzyltriethylammonium bromide, benzyltriethyl ammonium chloride,benzyltrimethylammonium bromide, benzyltrimethylammonium dichloroiodate,bis(triphenylphosphoranylidene)ammonium chloride,(dodecyldimethyl-2-phenoxyethyl)ammonium bromide,(diisobutylphenoxyethoxyethyl)dimethylbenzyl ammonium chloride,(4-nitrobenzyptrimethyl ammonium chloride, trimethylphenylammoniumbromide, trimethylphenylammonium chloride,(vinylbenzyl)trimethylammonium chloride,3-benzyl-5-(2-hydroxyethyl)-4-methylthiazolium chloride,1,1-dimethyl-4-phenylpiperazinium iodide, and the like. In anembodiment, the aryl compound is an aryl phosphine such as one of theaforementioned phosphines and the like. In an embodiment, the heteroarylquaternary ammonium salt includes a heteroaryl group instead of the arylgroup in the aryl quaternary ammonium salt here. Exemplary heteroarylquaternary ammonium salts include pyridyl(methyl)ammonium chloride(bromide, iodide), chinolinyl(methyl)ammonium chloride (bromide,iodide), benzothiophenyl(methyl)ammonium chloride (bromide, iodide), andthe like.

Exemplary aryl quaternary phosphonium salts includebenzyltriphenylphosphonium chloride, dimethyldiphenylphosphonium iodide,ethyltriphenylphosphonium iodide, methyltriphenoxyphosphonium iodide,tetraphenylphosphonium bromide, and the like. additional quaternaryphosphonium salts includes those derived from commercially available(Sigma Aldrich co.) phosphines such as substituted or unsubstitutedtriphenylphosphine, naphthyldiphenylphosphine,dinaphthylphenylphosphine, trinaphthylphosphine,9-anthryldiphenylphosphine, 9-anthryldinaphthylphosphine,diphenylpyrenylphosphine, dinaphthylpyrenylphosphine,bis(pentafluorophenyl)phenylphosphine, (4-bromophenyl)diphenylphosphine,4-(dimethylamino)phenyldiphenylphosphine,diphenyl(2-methoxyphenyl)phosphine,diphenyl(pentafluorophenyl)phosphine, 2-(diphenylphosphino)benzaldehyde,diphenyl-2-pyridylphosphine, diphenyl(p-tolyl)phosphine,tri-2-furylphosphine, tris(4-chlorophenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine, tris(4-fluorophenyl)-phosphine,tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,tris(pentafluoro-phenyl)phosphine,tris(2,4,6-trimethoxyphenyl)phosphine,tris(2,4,6-trimethylphenyl)phosphine, 2-(diphenylphosphino)benzoic acid,4-(diphenylphosphino)benzoic acid,4,4′-(phenyl-phosphinidene)bis(benzenesulfonic acid),3,3′,3″-phosphinidynetris(benzenesulfonic acid), tri-m-tolylphosphine,tri-o-tolylphosphine, tri-p-tolylphosphine,(1,2-bis(diphenyl-phosphino)benzene),(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and the like. Thesephosphines can be processed to produce aryl quaternary phosphonium saltsas described in U.S. patent application Ser. No. 10/553,307, thedisclosure of which is incorporated herein in its entirety. In anembodiment, the heteroaryl quaternary phosphonium salt includes aheteroaryl group instead of the aryl group in the aryl quaternaryphosphonium salts here. Exemplary heteroaryl quaternary phosphoniumsalts include pyridyl(methyl)phosphonium chloride (bromide, iodide),chinolinyl(methyl)phosphonium chloride (bromide, iodide),benzothiophenyl(methyl)phosphonium chloride (bromide, iodide), and thelike.

The anion X⁻ of the aromatic compound of formula (1) (e.g., the arylquaternary ammonium salt, heteroaryl quaternary ammonium salt, arylquaternary phosphonium salt, or heteroaryl quaternary phosphonium salt)can be a halide, triflate, sulfate, nitrate, hydroxide, carbonate,bicarbonate, acetate, phosphate, oxalate, cyanide, aklylcarboxylate,N-hydroxysuccinimide, N-hydroxybenzotriazole, alkoxide, thioalkoxide,alkane sulfonyloxide, halogenated alkane sulfonyloxide,arylsulfonyloxide, heteroarylsulfonyloxide bisulfate, valerate, oleate,palmitate, stearate, laurate, borate, benzoate, lactate, citrate,maleate, fumarate, succinate, tartrate, naphthylate, mesylate,glucoheptonate, lactobionate, and the like.

Exemplary aryl alkoxy silanes includestert-butoxy(chloro)diphenylsilane, amino phenyltrimethoxysilane,2-(4-pyridylethyl)triethoxysilane, 2-(trimethoxysilylethyl)pyridine,n-(3-trimethoxysilylpropyl)pyrrole,3-(m-aminophenoxy)propyltrimethoxy-silane,n-phenylaminopropyltrimethoxy-silane,(phenylaminomethyl)methyl-dimethoxysilane,n-phenylaminomethyltriethoxysilane, 3-(n-styrylmethyl-2-amino ethylamino)-propyltrimethoxysilane hydrochloride,(2-n-benzylaminoethyl)-3-amino propyl-trimethoxysilane hydrochloride,n-(3-triethoxysilylpropyl)-4,5-dihydroimidazole,2-(2-pyridylethypthiopropyltrimethoxysilane,2-(4-pyridylethyl)thiopropyltrimethoxysilane,benzoyloxypropyltrimethoxysilane,((chloromethyl)phenylethyl)-trimethoxysilane,(p-chloromethyl)phenyltrimethoxysilane,((chloromethyl)phenylethyl)-methyldimethoxysilane, b is(2-diphenylphosphinoethyl)-methylsilylethyltriethoxysilane,diphenylphosphinoethyldimethyl-ethoxysilane,2-(diphenylphosphino)ethyl-triethoxysilane,2-(2-pyridylethyl)thiopropyltrimethoxysilane,2-(4-pyridylethyl)thiopropyltri-methoxysilane,2-(3-trimethoxysilylpropylthio)-thiophene, 3-(n-styrylmethyl-2-aminoethyl amino)-propyltrimethoxysilane,(3-cyclopentadienylpropyl)triethoxysilane, styrylethyltrimethoxysilane,3-(2,4-dinitrophenyl amino)propyl-triethoxysilane,2-hydroxy-4-(3-methyldiethoxysilyl-propoxy)diphenylketone,2-hydroxy-4-(3-triethoxysilylpropoxy)-diphenylketone,o-4-methylcoumarinyl-n-[3-(triethoxy-silyl)propyl]carbamate,7-triethoxysilylpropoxy-5-hydroxy-flavone, 5-dimethylamino-n-(3-triethoxysilylpropyl)-napthalene-1-sulfonamide,2-(2-triethoxysilylpropoxy-5-methyl-phenyl)benzotriazole,3-(triethoxysilylpropyl)-p-nitro-benzamide,(R)-n-triethoxysilylpropyl-o-quinine-urethane,(R)-n-1-phenylethyl-n′-triethoxysilyl-propylurea,(S)-n-1-phenylethyl-n′-triethoxysilyl-propylurea, and the like availablefrom Gelest Inc, Morrisville, Pa. In an embodiment, the heteroarylalkoxy silanes include a heteroaryl group instead of the aryl group inthe aryl alkoxy silane compounds here. Exemplary heteroaryl alkoxysilanes include pyridylmethyltriethoxy silane,furylethyltriethoxysilane, thiophenylethyltriethoxy silane, and thelike.

Exemplary aryl halides include phenyl chloride, 2-chlorotoluene,2-bromotoluene, 4-chlorotoluene, 4-bromotoluene,2-chloro-4-methylnaphthalene, 2-bromo-4-methylnaphthalene,4-chloroanisole, 4-bromoanisole, 2-chlorobenzyl(2-methoxy)ethyl ether,2-bromobenzyl(2-methoxy)ethyl ether, 2-chlorobenzyl methyl ether,2-bromobenzyl methyl ether, 2-chlorobenzyl ethyl ether, 2-bromobenzylethyl ether, chlorobenzene, bromobenzene, iodobenzene, fluorobenzene,dichlorobenzene, trichlorobenzene, chlorotoluene, 2,4-dichlorotoluene,chloronaphthalene, bromonaphthalene, iodotoluenes, iodonaphthalene,2-bromo-6-methoxynaphthalene, 4-bromo-isobutylbenzene, triphenylmethanechloride, iodobenzene, bromotoluene, iodonaphthalene, chlorobenzene,phenylphosphine dichloride, diphenylphosphine mono chloride,(o-chlorophenyl)phosphine dichloride, bis(o-chlorophenyl)phosphinemonochloride, 1-naphthylphosphine bromides, chlorotolylphosphinechlorides, dichlorotolylphosphine chlorides, and the like. In anembodiment, the heteroaryl halide includes a heteroaryl group instead ofthe aryl group in the aryl halide compounds here, e.g.,2,6-dichloropyridine. Exemplary heteroaryl halides include pyridylethylchloride, furylethyl chloride, thiophenylethyl chloride, and the like.

In the composition, the functionalized silicate nanoparticle includes asilicate nanoparticle. The silicate nanoparticle contains silicon andoxygen that can be arranged in various structures such as a tetrahedralconfiguration and can have a shape such as a platelet, sphere,polyhedron, rod, cylinder, a combination thereof, and the like.According to an embodiment, the silicate nanoparticle comprises asilsesquioxane, cyclosilicate, inosilicate, nesosilicate,phyllosilicate, sorosilicate, tectosilicate, or a combination thereof.

The silicate nanoparticles, from which the composition is formed, aregenerally particles having an average particle size, in at least onedimension, of less than one micrometer (μm). As used herein “averageparticle size” refers to the number average particle size based on thelargest linear dimension of the particle (sometimes referred to as“diameter”). Particle size, including average, maximum, and minimumparticle sizes, may be determined by an appropriate method of sizingparticles such as, for example, static or dynamic light scattering (SLSor DLS) using a laser light source. Silicate nanoparticles can includeboth particles having an average particle size of 250 nm or less, andparticles having an average particle size of greater than 250 nm to lessthan 1 μm (sometimes referred in the art as “sub-micron sized”particles). In an embodiment, a silicate nanoparticle can have anaverage particle size of about 0.1 nanometers (nm) to about 500 nm,specifically 0.5 nm to 250 nm, more specifically about 1 nm to about 150nm, more specifically about 1 nm to about 125 nm, and still morespecifically about 1 nm to about 75 nm. The silicate nanoparticles maybe monodisperse, where all particles are of the same size with littlevariation, or polydisperse, where the particles have a range of sizesand are averaged. Generally, polydisperse silicate nanoparticles areused. Silicate nanoparticles of different average particle size may beused, and in this way, the particle size distribution of the silicatenanoparticles can be unimodal (exhibiting a single size distribution),bimodal (exhibiting two size distributions), or multi-modal (exhibitingmore than one particle size distribution).

The minimum particle size for the smallest 5 percent of the silicatenanoparticles can be less than 2 nm, specifically less than or equal to1 nm, and more specifically less than or equal to 0.5 nm. Similarly, themaximum particle size for 95% of the silicate nanoparticles can begreater than or equal to 900 nm, specifically greater than or equal to750 nm, and more specifically greater than or equal to 500 nm. Thesilicate nanoparticles can have a high surface area of greater than 300m²/g, and in a specific embodiment, 300 m²/g to 1800 m²/g, specifically500 m²/g to 1500 m²/g. In a particular embodiment, the silsesquioxanehas a size from 0.5 nm to 10 nm.

According to an embodiment, the silicate nanoparticle is asilsesquioxane. Silsesquioxanes, also referred to aspolysilsesquioxanes, polyorganosilsesquioxanes, or polyhedral oligomericsilsesquioxanes (POSS), are polyorganosilicon oxide compounds of generalformula RSiO_(1.5) (where R is a hydrogen, inorganic group, or organicgroup) having defined closed or open cage structures (closo or nidostructures, which are called respectively completely condensed orincompletely condensed structures). Silsesquioxanes can be prepared byacid and/or base-catalyzed condensation of functionalizedsilicon-containing monomers such as tetraalkoxysilanes includingtetramethoxysilane and tetraethoxysilane, alkyltrialkoxysilanes such asmethyltrimethoxysilane and methyltrimethoxysilane, as well as othergroups.

In an embodiment, the silsesquioxane has a closed cage structure, anopen cage structure, or a combination thereof. The silsesquioxane canhave any shape of cage structure such as cubes, hexagonal prisms,octagonal prisms, decagonal prisms, dodecagonal prisms, and the like.Additionally, the cage structure of the silsesquioxane comprises from 4to 30 silicon atoms, specifically, 4 to 20 silicon atoms, and morespecifically 4 to 16 silicon atoms, with each silicon atom in the cagestructure being bonded to oxygen. It should be noted that the term “cagestructure” is meant to include the SiO_(1.5) portion of the generalsilsesquioxane formula RSiO1.5, and not the R-group.

According to an embodiment, the silsesquioxane comprises a functionalgroup bonded to a silicone atom of the silsesquioxane. In a specificembodiment, the functional group bonded to the silicon atom comprises analkyl, alkoxy, haloakyl, cycloalkyl, heterocycloalkyl, cycloalkyloxy,aryl, aralkyl, aryloxy, aralkyloxy, heteroaryl, heteroaralkyl, alkenyl,alkynyl, amine, alkyleneamine, aryleneamine, alkenyleneamine, hydroxy,carboxyl, ether, epoxy, ketone, halogen, hydrogen, or a combinationthereof. Thus, the silsesquioxane derivatized with a functional groupincludes a group such as an alcohol, amine, carboxylic acid, epoxy,ether, fluoroalkyl, halide, imide, ketone, methacrylate, acrylate,silica, nitrile, norbornenyl, olefin, polyethylene glycol (PEG), silane,silanol, sulfonate, thiol, and the like. Furthermore, the silsesquioxanecan have from one functional group to as many functional groups as thereare silicon atoms in the cage structure of the silsesquioxane. In aspecific embodiment, the silsesquioxane is a derivatizedoctasilsesquioxane R_(8-n)H_(n)(SiO_(1.5))₈ (where 0≤n≤8, and R can be asame or different functional group), and the number of functional groupsvaries with the number of silicon atoms in the cage structure, i.e.,from 0 to 8 functional groups.

Exemplary silsesquioxanes having a closed cage structure include1-allyl-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-allyl-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-[3-(2-aminoethyl)amino]propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1 (5,15).1(7,13)]octasiloxane;1-chlorobenzylethyl-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(4-chlorobenzyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-chloropropyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15). 1(7,13)]octasiloxane;(cyanopropyldimethylsilyloxy)heptacyclopentylpentacyclooctasiloxane;1-(2-trans-cyclohexanediopethyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1 (5,15).1(7,13)]octasiloxane;1-(3-cyclohexen-1-yl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; dodecaphenyl-dodecasiloxane;1-[2-(3,4-epoxycyclohexyl)ethyl]-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13-heptacyclopentyl-15-glycidylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(3-glycidyl)propoxy-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1 (5,15).1(7,13)]octasiloxane; octakis(tetramethyl ammonium)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane-1,3,5,7,9,11,13,15-octakis(yloxide)hydrate; 3-hydroxypropylheptaisobutyl-octasiloxane;1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9). 1(5,15).1(7,13)]octasiloxane;octacyclohexenylethyldimethylsilyloxy-octasiloxane;1,3,5,7,9,11,13,15-octacyclohexylpentacyclooctasiloxane;octa[(1,2-epoxy-4-ethylcyclohexyl)dimethylsiloxy]octasiloxane;octa[(3-glycidyloxypropyl)dimethylsiloxy]octasiloxane;octa[(3-hydroxypropyl)dimethylsiloxy]octasiloxane;1,3,5,7,9,11,13,15-octakis[2-(chlorodimethylsilyl)ethyl]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octamethylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane; 1,3,5,7,9,11,13,15-octaphenylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octa(2-trichlorosilyl)ethyl)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octavinylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(2,3-propanediol)propoxy-3,5,7,9,11,13,15-isobutylpentacyclo-[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl)propylmethacrylate;(3-tosyloxypropyl)-heptaisobutyloctasiloxane;1-(trivinylsilyloxy)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-vinyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane,(3-(2,2-bis(hydroxymethyl)butoxy)propyl)dimethylsiloxy-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1.(3,9).1(5,15).1(7,13)]octasiloxane;octa(3-hydroxy-3-methylbutyldimethylsiloxy)octasiloxane;1-(3-amino)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1.(3,9).1(5,15).1(7,13)]octasiloxane;1-(3-amino)propyl-3,5,7,9,11,13,15-isooctylpentacyclo[9.5.1.1. (3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octaaminophenylpentacyclo[9.5.1(3,9).1(5,15).1(7,13)]octasiloxane;octa-n-phenylaminopropyl)-octasiloxane;n-methylaminopropyl-heptaisobutyl-octasiloxane;octaethylammoniumoctasiloxane chloride;1-(4-amino)phenyl-3,5,7,9,11,13,15-cyclohexlpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(amino)phenyl-3,5,7,9,11,13,15-cyclohexlpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(4-amino)phenyl-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(amino)phenyl-3,5,7,9,11,13,15-heptaisobutylpentacylco[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-[(3-maleamicacid)propyl]-3,5,7,9,11,13,15-heptacyclohexylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-octasiloxane;1-[(3-maleamicacid)propyl]-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-octasiloxane;octamaleamic acid octasiloxane;trimethoxy-[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane, hydrolyzed;2-[[3-(trimethoxysilyl)propoxy]methyl]-oxirane, hydrolyzed; ethyl3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane-1-undecanoate;1-(3-glycidyl)propoxy-3,5,7,9,11,13,15-isooctylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsilyloxy}-1,3,5,7,9,11,14-heptacyclohexyltricyclo[7.3.3.1(5,11)]heptasiloxane;3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsilyloxy}-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane;octatrifluoropropyloctasiloxane;endo-3,7,14-trifluoropropyl-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane;1-chlorobenzyl-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15). 1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octakis(1,2-dibromoethyl)-pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-[(3-maleimide)propyl]-3,5,7,9,11,13,15-heptacyclohexylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]-octasiloxane;1-[(3-maleimide)propyl]-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15). 1(7,13)]-octasiloxane;3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 (3,9).1(5,15).1(7,13)]octasiloxan-1-yl)propylacrylate;3-[3,5,7,9,11,13,15-heptacyclohexylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl]methylmethacrylate;3-[3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1 (3,9).1(5,15).1(7,13)]octasiloxan-1-yl]methylmethacrylate;3-[3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl]methylmethacrylate;3-[3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl]propylmethacrylate;3-[3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1yl]methylmethacrylate;3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl)propylmethacrylate;3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxan-1-yl)propylmethacrylate;octasiloxa-octapropylmethacrylate; octasiloxa-octapropylacrylate;dodecaphenyldecasiloxane; octaisooctyloctasiloxane;phenylheptaisobutyloctasiloxane; phenylheptaisooctyloctasiloxane;isooctylhetpaphenyloctasiloxane; octaisobutyloctasiloxane;octamethyloctasiloxane; octaphenyloctasiloxane;octakis(tetramethylammonium)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane1,3,5,7,9,11,13,15-octakis(cyloxide)hydrate;octakis(trimethylsiloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane-1-butyronitrile;1-[2-(5-norbornen-2-yl)ethyl]-3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1(3,9).1(7,13)]octasiloxane;1-[2-(5-norbornen-2-yl)ethyl]-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(7,13)]octasiloxane;1-allyl-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1(3,9).1(7,13)]octasiloxane;1,3,5,7,9,11,13-heptaisobutyl-15-vinylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octa[2-(3-cyclohexenyl)ethyldimethylsiloxy]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octavinylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octa[vinyldimethylsiloxy]pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)pentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1,3,5,7,9,11,13,15-octahydropentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;1-(3-mercapto)propyl-3,5,7,9,11,13,15-isooctylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane;and the like.

Exemplary silsesquioxanes having an open cage structure include1,3,5,7,9,11,14-heptacyclohexyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11-octaisobutyltetracyclo[7.3.3.1(5,11)]octasiloxane-endo-3,7-diol;1,3,5,7,9,11,14-heptaethyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11,14-heptaisooctyltricyclo[7.3.3.1(5,110]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;tricyclo[7.3.3.3(3,7)]octasiloxane-5,11,14,17-tetraol-1,3,5,7,9,11,14,17-octaphenyl;9-{dimethyl[2-(5-norbornen-2-yl)ethyl]silyloxy}-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.15,11]heptasiloxane-1,5-diol;endo-3,7,14-tris{dimethyl[2-(5-norbornen-2-yl)ethyl]silyloxy}-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane;[[dimethyl(trifluoromethyl)ethyl]silyloxy]heptacyclopentyltricycloheptasiloxanediol;1,3,5,7,9,11,14-heptacyclohexyltricyclo[7.3.3.1(5,11)]heptasiloxane-3,7,14-triol;1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;1,3,5,7,9,11-octacyclopentyltetracyclo[7.3.3.1(5,11)]octasiloxane-endo-3,7-diol;1,3,5,7,9,11,14-hepta-isooctyltricyclo[7.3.3.1(5,11)]heptasiloxane-endo-3,7,14-triol;endo-3,7,14-trifluoro-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane; endo-3,7,14-tris{dimethyl[2-(5-norbornen-2-yl)ethyl]silyloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane;tris((dimethyl(trifluoromethyl)ethyl)silyloxy)heptacyclopentyltricycloheptasiloxane;3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsilyloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.1(5,11)]heptasiloxane,and the like.

A combination of the silsesquioxanes with an open cage structure orclosed cage structure can be used as the silsesquioxane in conjunctionwith a combination of any of the other silicate nanoparticles.

In an embodiment, the silicate nanoparticle is a silicate mineral suchas cyclosilicate, inosilicate, nesosilicate, phyllosilicate,sorosilicate, tectosilicate, or a combination thereof.

Cyclosilicates are silicates with tetrahedrons that can link to formrings of three (Si₃O₉)⁻⁶, four (Si₄O₁₂)⁻⁸, six (Si₆O₁₈)⁻¹² or nine(Si₉O₂₇)⁻¹⁸ units. Exemplary cyclosilicates include benitoite, axinite,beryl, cordierite, tourmaline, papagoite, eudialyte, milarite, and thelike.

The inosilicate can have a crystalline structure in the form of a chainsuch as pyroxenes and pyroxenoids (with a crystalline structure ofsingle chains (SiO₃)⁻²) or amphiboles (with a crystalline structure ofdouble chains (Si₄O₁₁)⁻⁶). Non-limiting examples of pyroxenes andpyroxenoids include diopside, spodumene, wollastonite, enstatite,hypersthene, hedenbergite, augite, pectolite, diallage, fassaite,spodumene, jeffersonite, aegirine, omphafacite, hiddenite, and the like.Non-limiting examples of amphiboles are calcium amphiboles such astremolite, actinote, and hornblende; iron-magnesium amphiboles such asgrunerite and cummingtonite; and sodium amphiboles such as glaucophane,arfvedsonite and riebeckite; and the like.

Non-limiting examples of nesosilicates are alite, almandine,andalousite, andalusite, andradite, belite, chloritoid, chondrodite,clinohumite, datolite, dumortierite, fayalite, forsterite, grossular,humite, hydrogrossular, kyanite, norbergite, olivine, phenakite, pyrope,sillimanite, spessartine, staurolite, thaumasite, thorite, titanite,topaz, uvarovite, zircon, and the like.

The phyllosilicate can be a clay, mica, serpentine, chlorite, or acombination thereof. Exemplary phyllosicates include antigorite,biotite, chlorite, chrysotile, glauconite, halloysite, illite,kaolinite, lepidolite, lizardite, margarite, montmorillonite, muscovite,palygorskite, phlogopite, pyrophyllite, talc, vermiculite, and the like.

The soro silicate can be allanite, clinozoisite, dollaseite, epidote,hemimorphite, ilvaite, lawsonite, prehnite, tanzanite, vesuvianite,zoisite, and the like.

The tectosilicate can be, for example, albite, alkali-feldspars,analcime, andesine, anorthite, anorthoclase, bytownite, cancrinite,celsiane, chabazite, coesite, cristobalite, feldspar, feldspathoid,hauyne, heulandite, labradorite, lazurite, leucite, marialite, meionite,microcline, mordenite, natrolite, nepheline, nosean, oligoclase,orthoclase, petalite, plagioclase, quartz, sanidine, scapolite,scolecite, silica, sodalite, stilbite, tridymite, zeolite, and the like.

Exemplary zeolites include naturally occurring zeolites such as amicite,analcime, barrerite, bellbergite, bikitaite, boggsite, brewsterite,chabazite, clinoptilolite, cowlesite, dachiardite, edingtonite,epistilbite, erionite, faujasite, ferrierite, garronite, gismondine,gmelinite, gobbinsite, gonnardite, goosecreekite, harmotome,herschelite, heulandite, laumontite, levyne, maricopaite, mazzite,merlinoite, mesolite, montesommaite, mordenite, natrolite, offretite,paranatrolitem, paulingite, pentasil, perlialite, phillipsite,pollucite, scolecite, sodium dachiardite, stellerite, stilbite,tetranatrolite, thomsonite, tschernichite, wairakite, wellsite,willhendersonite, and yugawaralite. In some embodiments, the zeolite isanalcime, chabazite, clinoptilolite, heulandite, natrolite, phillipsite,stilbite, or a combination thereof. A synthetic zeolite also can be usedas the tectosilicate of the silicate nanoparticle. The syntheticzeolites can be selected from Zeolite A, Zeolite B, Zeolite F, ZeoliteH, Zeolite L, Zeolite T, Zeolite W, Zeolite X, Zeolite Y, Zeolite Omega,Zeolite ZSM-5, Zeolite ZSM-4, Zeolite P, Zeolite N, Zeolite D, ZeoliteO, Zeolite S, and Zeolite Z.

In an embodiment, the silicate nanoparticle can include other elementsor components in addition to silicon and oxygen. The silicatenanoparticle can include an oxide, for example, silicon dioxide (SiO₂),aluminum oxide (A₁₂O₃), barium oxide (BaO), bismuth trioxide (Bi₂O₃),boron oxide (B₂O₃), calcium oxide (CaO), cesium oxide (CsO), lead oxide(PbO), strontium oxide (SrO), rare earth oxides (e.g., lanthanum oxide(La₂O₃), neodymium oxide (Nd₂O₃), samarium oxide (Sm₂O₃), cerium oxide(CeO₂)), and the like. An exemplary silicate nanoparticle containingSiO₂ includes quartz, cristobalite, tridymite, and the like. The otherelements can be, for example, aluminum, antimony, arsenic, barium,beryllium, boron, calcium, cerium, cesium, chromium, cobalt, copper,gallium, gold, iron, lanthanum, lead, lithium, magnesium, manganese,molybdenum, neodymium, nickel, niobium, palladium, phosphorus, platinum,potassium, praseodymium, silver, sodium, tantalum, thorium, titanium,vanadium, zinc, zirconium, and the like. The other elements can occur inthe silicate nanoparticle in the form of oxides, carbonates, nitrates,phosphates, sulfates, or halides. Furthermore, the other element can bea dopant in the silicate nanoparticle.

It is contemplated that the silicate nanoparticle is functionalized withthe functionalization compound or a chemical group from thefunctionalization compound. Functionalization of the silicatenanoparticle to form the functionalized silicate nanoparticle can beachieved by a cation exchange reaction, substitution, condensation,alkoxysilane chemistry, and the like. Without wishing to be bound by thetheory, the silicate nanoparticle can have a group such as a hydroxygroup on its surface that interacts with and can react with thefunctionalization compound or chemical group thereof. As used herein,the bond of the first portion of the chemical group includes covalentbonds as well as ionic bonds.

As noted above, the functionalization compound includes a chemical groupthat has a first portion and a second portion, which includes anaromatic moiety or a nonaromatic moiety. The first portion is directlybonded to the silicate nanoparticle in the functionalized silicatenanoparticle. In terms of formulas (1), (2), and (3), the second portionincludes the aromatic or nonaromatic moiety Ar. Also, the first portioncan include the A group (e.g., nitrogen or phosphorous), Si, oxygen(—O—), or linker group L in formulas (1), (2), and (3). As used herein,the bond of the first portion of the chemical group includes covalentbonds as well as ionic bonds.

The compounds of formulas (4)-(7) can be attached to the silicatenanoparticles through an ionic bond via “N” or “S.” In this instant, thefirst portion of the chemical group which functionalizes the silicatenanoparticle is an ionic bond and the second portion of the chemicalgroup is a cation of formula (4), formula (5), formula (6) or formula(7). The compounds of formula (8) can be attached to the silicatenanoparticle through Si when R₂₅ is halide or when R₂₅ is an alkoxygroup.

In an embodiment, the functionalization compound is a compound offormula (2) in which the central silicon atom is bonded to the silicatenanoparticle. In an embodiment, the aromatic compound of formula (1) isbonded to the silicate nanoparticle via directly bonding the A group tothe silicate nanoparticle.

In another embodiment, the chemical group is derived from a compound offormula (1), (2), (3), (4), (5), (6), (7), or (8). In a specificembodiment, the chemical group is derived from a quaternary ammoniumsalt, quaternary phosphonium salt, alkoxy silane, halide, a guanidine, aguanidinium salt, a biguanidinium salt, or a sulfonium salt. Here, thechemical group can be derived from the functionalization compound (e.g.,by hydrolysis, photolytic cleavage, thermal decomposition, elimination,substitution, etc.) to produce the chemical group including the aromaticor nonaromatic moiety Ar with or without the linker group L, such thatthe chemical group is bonded to the silicate nanoparticle. In formula(1), the bond between the A group and linker group, moiety Ar, or Rgroup is broken. In formula (2), the bond between the Si atom and oxygenatom (—O—), linker group L, moiety Ar, or R group is broken. In formula(3), the bond between the halogen X and linker group or moiety Ar isbroken. Thus, in an embodiment, the moiety Ar is directly bonded to thesilicate nanoparticle. Alternatively, the linker group L can remainattached to the moiety Ar such that the linker group L is directlybonded to the silicate nanoparticle with the moiety Ar indirectly bondedto the silicate nanoparticle via the linker group L. In an embodiment,the R group is directly bonded to the silicate nanoparticle.Consequently, it is contemplated that the linker group L can be disposedbetween the silicate nanoparticle and the second portion of the chemicalgroup in the functionalized silicate nanoparticle. Thus, thefunctionalized silicate nanoparticle can be a reaction product of thesilicate nanoparticle with the aromatic or nonaromatic compound,chemical group derived from the aromatic or nonaromatic compound, or acombination thereof.

In an embodiment, the functionalized silicate nanoparticle can beprepared by contacting the silicate nanoparticle with thefunctionalization compound or chemical group thereof under conditionseffective to functionalize the silicate nanoparticle. The chemical groupcan be prepared by subjecting the functionalization compound toconditions effective to break bonds within the functionalizationcompound with a product fragment being the chemical group comprising thefirst and second portions herein. Conditions include those oftemperature, pressure, catalysis (e.g., acid catalysis, metal catalysis,support (e.g., zeolite) promotion, and the like), and the like. Aftercontact of the silicate nanoparticle with the aromatic compound orchemical group, the aromatic compound or chemical group is bonded to thesilicate nanoparticle to form the functionalized silicate nanoparticle.

In a particular embodiment, an aryl alkoxy silane (e.g.,trimethyl(2-phenylethoxy)silane contacts a silicate nanoparticle clay(e.g., montmorillonite), and the silicon of thetrimethyl(2-phenylethoxy)silane bonds to the montmorillonite to form afunctionalized silicate nanoparticle, having a phenyl ring extendingfrom the surface of the montmorillonite to form a phenyl terminatedfunctionalization. In another embodiment, thetrimethyl(2-phenylethoxy)silane is subjected to a lysis condition toproduce an aromatic moiety of a (2-phenylethyl)oxidanyl radical, whichsubsequently bonds to the montmorillonite to form the functionalizedsilicate nanoparticle, having a phenyl ring extending from the surfaceof the montmorillonite to form a phenyl terminated functionalization.Here, the linker group is —CH₂O—, which is directly bonded to thesilicate nanoparticle via oxygen (O) and directly bonded to the phenylring by the methylene (—CH₂—).

In another embodiment, a heteroaryl quaternary ammonium salt (e.g.,N,N-dimethyl-N-(pyridine-3-ylmethyl)ethanaminium chloride (DMPME))contacts a silicate nanoparticle silsesquioxane (e.g.,1-allyl-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane). The resulting functionalizedsilicate nanoparticle includes the silsesquioxane directly bonded to theamino nitrogen of the DMPME with the pyridinyl ring extending (via themethylene amino (—CH₂N—) linker group) from the surface of the DMPME toform a pyridinyl terminated functionalization.

The composition is effective to remove an asphaltene particle from asubstrate such as a metal, composite, sand, rock, mineral, glass,formation, downhole element, or a combination thereof. Without wishingto be bound by theory, it is believed that the functionalized silicatenanoparticle is an amphiphile (i.e., having hydrophilic and lipophilicportions) and interacts with both the substrate and the asphalteneparticle. It is contemplated that, within the functionalized silicatenanoparticle, the silicate nanoparticle is hydrophilic with a greateraffinity for the substrate than the asphaltene particle, and thearomatic or nonaromatic functionalization (either aryl or heteroarylterminated functionalization) is lipophilic with a greater affinity forthe asphaltene particle than the substrate. Moreover, the asphalteneparticle has a greater affinity for the aromatic or nonaromaticfunctionalization of the functionalized silicate nanoparticle than thesilicate nanoparticle portion of the functionalized silicatenanoparticle or the substrate.

In an embodiment, in addition to the functionalized silicatenanoparticle, the composition also includes a fluid. The fluid can bepresent in an amount to increase a separation and aid removal of theasphaltene particle from the substrate. That is, while thefunctionalized silicate nanoparticle separates or removes the asphalteneparticle from the substrate, the fluid can sweep the removed asphalteneparticle (which has been desorbed from the substrate) away from alocation proximate to the substrate. In an embodiment, the fluid canalso aid in separating the asphaltene particle from the substrate. In anembodiment, the asphaltene particle has a greater affinity for the fluidthan the substrate or the silicate nanoparticle portion of thefunctionalized silicate nanoparticle.

Exemplary fluids include water (liquid or steam), oil, carbon dioxide,C1-C6 alkane (e.g., gaseous or liquefied at a temperature or pressure ofthe surrounding environment of the composition), tetrahydrofuran,1,4-dioxane; diglyme, triglyme, acetonitrile, propionitrile,benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, nitrobenzene, sulfolane, acetone, butanone,cyclohexanone, diethyl ketone, methyl isobutyl ketone, 2-pentanone,2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 3-pentanone, brine,completion fluid, acid, base, gas, polar solvent, nonpolar solvent, or acombination thereof. Additional exemplary fluids also include thosetypically encountered downhole, such as hydrocarbons, solvents, or anaqueous environment that includes formation water, seawater, salt (i.e.,brine, including formates and inorganic salts, e.g., NaCl, KCl, CaCl₂,MgCl₂, CaBr₂, ZnBr₂, NaBr, and the like), completion brine, stimulationtreatment fluid, remedial cleanup treatment fluid, acidic or corrosiveagent such as hydrogen sulfide, hydrochloric acid, or other suchcorrosive agents, or a combination thereof. Solvents include aninorganic solvent, organic solvent, or a combination thereof. Exemplarysolvents include water, alcohols (e.g., methanol, ethanol, and thelike), polyhydric alcohols (e.g., diethylene glycol, dipropylene glycol,1,2-propanediol, 1,4-butanediol, 1,3-butanediol, glycerol,1,5-pentanediol, 2-ethyl-1-hexanol, and the like), ketones (e.g.,acetophenone, methyl-2-hexanone, and the like), ethers (e.g., ethyleneglycol monobutyl ether, triethylene glycol monomethyl ether, and thelike), carboxylic acid esters (e.g., [2,2-butoxy(ethoxy)]ethyl acetateand the like), esters of carbonic acid (e.g., propylene carbonate andthe like), inorganic acids (e.g., hydrofluoric acid, hydrochloric acid,phosphoric acid, sulfuric acid, nitric acid, and the like), organicacids (e.g., those having an C1-C10 alkyl chain, which is a straight orbranched chain and can be substituted), or a combination thereof.

The brine can be, for example, seawater, produced water, completionbrine, or a combination thereof. The properties of the brine can dependon the identity and components of the brine. Seawater, as an example,contains numerous constituents such as sulfate, bromine, and tracemetals, beyond typical halide-containing salts. On the other hand,produced water can be water extracted from a production reservoir (e.g.,hydrocarbon reservoir), produced from the ground. Produced water is alsoreferred to as reservoir brine and often contains many components suchas barium, strontium, and heavy metals. In addition to the naturallyoccurring brines (seawater and produced water), completion brine can besynthesized from fresh water by addition of various salts such as NaCl,CaCl₂, or KCl to increase the density of the brine, such as 10.6 poundsper gallon of CaCl₂ brine. Completion brines typically provide ahydrostatic pressure optimized to counter the reservoir pressuresdownhole. The above brines can be modified to include an additionalsalt. In an embodiment, the additional salt included in the brine isNaCl, KCl, NaBr, MgCl₂, CaCl₂, CaBr₂, ZnBr₂, NH₄Cl, sodium formate,cesium formate, and the like. The salt can be present in the brine in anamount from about 0.5 wt. % to about 50 wt. %, specifically about 1 wt.% to about 40 wt. %, and more specifically about 1 wt. % to about 25 wt.%, based on the weight of the composition.

The density, polarity, hydrophilicity, lipophilicity, and the like ofthe fluid can be achieved by selection of the foregoing fluids. Theselection of the fluid can depend on, for example, a desired density forthe composition. In an embodiment, fluid is present in the compositionin an amount from about 1 weight percent (wt. %) to about 99 wt. %,specifically about 10 wt. % to about 90 wt. %, and more specificallyabout 20 wt. % to about 80 wt. %, based on the weight of thecomposition.

The composition can be prepared by combining the fluid with thefunctionalized silicate nanoparticle. In an embodiment, the fluid iscombined with the functionalization compound and silicate nanoparticlewith subsequent formation of the functionalized silicate nanoparticle.According to an embodiment, the functionalized silicate nanoparticle cancontact an asphaltene particle prior to addition of the fluid. In anembodiment, the silicate nanoparticle is contacted with the chemicalgroup (which includes the aromatic moiety) derived from thefunctionalization compound, such as by breaking a bond between thechemical group and the rest of the functionalization compound.Consequently, it will be appreciated that the functionalized silicatenanoparticle is a reaction product of the silicate nanoparticle and thefunctionalization compound or chemical group thereof.

In an embodiment, a method for making the functionalized silicatenanoparticle includes contacting the silicate nanoparticle with achemical group to form the functionalized silicate nanoparticle. Thechemical group includes a first portion and a second portion comprisingan aromatic or nonaromatic moiety. In forming the functionalizedsilicate nanoparticle, the first portion is directly bonded to thesilicate nanoparticle in the functionalized silicate nanoparticle. Thearyl or nonaromatic moiety extends from the surface of thefunctionalized silicate nanoparticle by the first portion.

The functionalized silicate nanoparticle herein has many uses andbeneficial properties. In an embodiment, the functionalized silicatenanoparticle is effective to remove an asphaltene particle or otheraromatic species from a substrate comprising a metal, composite, sand,rock, mineral, glass, formation, downhole element, or a combinationthereof.

According to an embodiment, an asphaltene particle, which is disposed ona substrate, can be removed from the substrate by contacting theasphaltene particle with the functionalized silicate nanoparticle. Thefunctionalized silicate nanoparticle can be interposed between theasphaltene particle and the substrate. The asphaltene particle can beseparated from the substrate with the functionalized silicatenanoparticle and removed from the substrate.

In an embodiment, the asphaltene particle can be exfoliated using thefunctionalized silicate nanoparticle. Without wishing to be bound bytheory, it is believed the aromatic moiety of the functionalizedsilicate nanoparticle can intercalate in a gallery of the asphalteneparticle. The functionalized silicate nanoparticle can be heated to atemperature effective to exfoliate the functionalized silicatenanoparticle, asphaltene particle, or a combination thereof. Accordingto an embodiment, the functionalized silicate nanoparticle expands uponheating. As a result of the expansion, a distance increases betweenneighboring aromatic moieties that are tethered to the functionalizedsilicate nanoparticle. The asphaltene particles expand and exfoliate inresponse to the increased distance between the neighboring aromaticmoieties of the functionalized silicate nanoparticle that areintercalated in the gallery of asphaltene molecules of the asphalteneparticle. Exfoliation of the asphaltene particle can occur forasphaltene particles attached to the substrate or for those asphalteneparticles that are not attached to a substrate.

The removal of the asphaltene particle from the substrate can alsoinclude contacting the asphaltene particle with a fluid. Here, contactof the fluid can increase a distance of separation between theasphaltene particle and the substrate before or after separating theasphaltene particle from the substrate.

Beneficially, the methods herein, e.g., contacting the silicatenanoparticle with the chemical group to form the functionalized silicatenanoparticle, can be performed in-situ in an environment such as apipeline, downhole, formation, tubular, frac feature (e.g., a vein orpore), production zone, reservoir, refinery, transport tube, productiontube, or a combination thereof. Moreover, the asphaltene particle orexfoliated asphaltene can be removed from the environment afterseparating the asphaltene particle from the substrate.

Furthermore, it has been found that perturbing the internal structure ofasphaltene particles, for example, in a micelle or other aggregate, canlead to increased quality of oil containing asphaltenes. Additionally,degradation of asphaltene aggregates herein enhances production ofpetroleum fluid in a downhole, subsurface, or ground environment.Furthermore, removal of asphaltene from pores of a rock formation,within a reservoir, or from a sidewall of a tubular, production tubing,borehole, or transportation tube can improve the permeability of suchstructures, leading to increased quality of oil as well as increased orprolonged lifetime for oil production.

In an embodiment, a method for decomposing an asphaltene particleincludes contacting the asphaltene particle with the functionalizedsilicate nanoparticle and causing the intercalating agent to increase adistance between asphaltene molecules in the asphaltene particle todecompose the asphaltene particle. As above, the aromatic moiety ornonaromatic moiety of the functionalized silicate nanoparticle can bedisposed in the gallery between adjacent asphaltene molecules ordisposed at the periphery of an asphaltene molecule such as proximate toan edge of an aromatic plane or terminal chain attached to an aromaticportion of an asphaltene molecule in the asphaltene particle. During theexfoliation of the asphaltene particle, the functionalized silicatenanoparticle portion in the gallery forces the adjacent asphaltenemolecules away from one another, thereby separating the asphaltenemolecules. In this manner, an asphaltene molecule can be exfoliated fromthe asphaltene particle.

As used herein, “decomposition” refers to an increased separationdistance between asphaltene molecules in an asphaltene particle,expansion of the volume of the asphaltene particle, complete removal ofan asphaltene molecule from an asphaltene particle, or a change in theelectronic structure or bonding in an asphaltene molecule in anasphaltene particle. Thus, decomposition includes, for example,deagglomeration, exfoliation, disaggregation, and the like. An exampleof a change in the electronic structure or bonding in an asphaltenemolecule in an asphaltene particle includes converting a bond (e.g.,converting a π bond to σ bond or vice versa), breaking a bond, orforming a bond.

Thus, according to an embodiment, the method includes exfoliating anasphaltene particle. In an embodiment, exfoliating includes removing anasphaltene molecule from the asphaltene particle. Exfoliation of anasphaltene particle, in an embodiment, decreases the number ofasphaltene molecules in the asphaltene particle. It will be appreciatedthat exfoliation of asphaltene particles can provide exfoliatedasphaltene as a single asphaltene molecule or as a micelle or layeredparticle containing fewer asphaltene molecules than the non-exfoliatedasphaltene particle.

In a further embodiment, the method includes increasing the temperatureof the functionalized silicate nanoparticle, asphaltene particle, orsubstrate. Increasing the temperature includes techniques that canelevate the temperature to about 60° C. to about 1200° C., specificallyabout 100° C. to about 1000° C., and more specifically about 100° C. toabout 800° C. Such techniques involve, for example, in-situ combustion,steam introduction, heated fluid injection, or a combination comprisingat least one of the foregoing. In an embodiment, a downhole environmentis heated by introducing steam in an injection well with the steampropagating through the formation and heating the functionalizedsilicate nanoparticle, asphaltene particle, or substrate. It iscontemplated that increasing the temperature can cause reaction,including decomposition of the functionalized silicate nanoparticle,substrate, or asphaltene particle. In addition, the asphaltene particlescan be heated to expand, decreasing the mutual attraction amongasphaltene molecules therein. Depending on the amount of expansion ofthe asphaltene particle, asphaltene molecules can exfoliate from theasphaltene particles. In one embodiment, the heating of a functionalizedsilicate nanoparticle associated with the asphaltene particle can leadto exfoliation of an asphaltene molecule therefrom.

Heated fluid injection can include heating a fluid (e.g., a solvent) andsubsequently disposing the heated fluid downhole to increase thetemperature of the asphaltene particles. In a non-limiting embodiment,in-situ combustion increases the temperature of the functionalizedsilicate nanoparticle by injecting a gas containing oxygen, for exampleair, downhole and igniting oil in the reservoir. The combustion releasesheat, which can be absorbed by the functionalized silicate nanoparticleor asphaltene particle, in order to exfoliate an asphaltene moleculefrom the asphaltene particle.

In certain embodiments, the method further includes applying sonicfrequencies to the intercalating agent. The sonic frequencies can befrom about 400 hertz (Hz) to about 400 megahertz (MHz), specificallyabout 800 Hz to about 350 MHz, and more specifically about 1 kilohertz(kHz) to about 300 MHz. A transducer placed near the asphaltene particlecan produce the sonic frequency, which can destructively interact withthe asphaltene particle or functionalized silicate nanoparticle. Sonicfrequencies may induce chemical reactions or expansion of thefunctionalized silicate nanoparticle and disrupt interparticle bondingin the asphaltene particle, leading to exfoliation of an asphaltenemolecule. The sonic frequencies can detach neighboring polyaromaticplanes of adjacent asphaltene molecules. Without wishing to be bound byany particular theory, such deterioration of the asphaltene particle maybe induced by short-lived, localized disturbances (e.g., a hot spot)produced by the implosion of bubbles in the course of acousticcavitation.

In some embodiments, the functionalized silicate nanoparticle isdispersed in a fluid. Such dispersion can occur before or aftercontacting the asphaltene particle with the functionalized silicatenanoparticle. The fluid can be an organic solvent, inorganic solvent, ora combination comprising at least one of the foregoing. Exemplary fluidsare those above and can include CH₃NO₂, CH₂Cl₂, CHCl₃, CCl₄, C₂H₄Cl₂,H₂O, SOCl₂, SO₂Cl₂, S₃N₃Cl₃, benzene, toluene, o-xylene, dimethylsulfoxide, furan, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane,dimethoxyethane, n-methyl-pyrrolidone, n,n-dimethylacetamide,γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, benzyl benzoate,hexafluorobenzene, octafluorotoluene, pentafluorobenzonitrile,pentafluoropyridine, pyridine, dimethylformamide,hexamethylphosphoramide, nitromethane, benzonitrile, or the like. In anembodiment, the fluid can react with the functionalized silicatenanoparticle to produce product compounds that decompose the asphalteneparticle.

In another embodiment, after contact with the functionalized silicatenanoparticle, the asphaltene particle can be heated. The heat isabsorbed by the asphaltene molecule, causing high amplitude vibrationalmotion of the non-polar groups, e.g., hydrocarbon tails that terminatean asphaltene molecule. In this manner, exfoliation of asphaltenemolecules can occur by vibrationally-mediated dissociation or furtherincreased spacing among the asphaltene molecules in the asphalteneparticle. Additionally, the heated asphaltene particles can be moremiscible with the fluid. Here, the fluid can be as before and caninclude, for example, an alkane, aromatic solvent, carbon dioxide,carbon disulfide, resin, oil, or a combination thereof. Particularfluids include, 2,2-dimethylpropane, butane, 2,2-dimethylbutane,pentane, hexane, heptane, octane, nonane, decane, unedecane,cyclopentane, cyclohexane, benzene, toluene, o-xylene, dimethylsulfoxide, furan, tetrahydrofuran, o-dioxane, m-dioxane, p-dioxane,dimethoxyethane, n-methyl-pyrrolidone, n,n-dimethylacetamide,γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, benzyl benzoate,hexafluorobenzene, octafluorotoluene, pentafluorobenzonitrile,pentafluoropyridine, pyridine, dimethylformamide,hexamethylphosphoramide, nitromethane, benzonitrile, and the like.

In another embodiment, a fluid or surfactant can contact the exfoliatedasphaltene particle and allow dispersion of the asphaltene particle, forexample, in an oil. Exemplary fluids include solvent such as a polarsolvent, aromatic solvent, or a combination comprising at least one ofthe foregoing. The polar solvent can be an alcohol (e.g., ethanol,propanol, glycol, and the like), amine (e.g., methylamine, diethylamine, tributyl amine, and the like), amide (e.g., dimethylformamide),ether (e.g., diethyl ether, polyether, tetrahydrofuran, and the like),ester (e.g., ethyl acetate, methyl butyrate, and the like), ketone(e.g., acetone), acetonitrile, dimethylsulfoxide, propylene carbonate,and the like. The aromatic solvent can be, for example, benzene,toluene, xylene, pyridine, hexafluorobenzene, octafluorotoluene,pentafluoropyridine, and the like.

The methods and materials herein can be used to enhance oil recovery ina reservoir, borehole, downhole, production zone, formation, or acombination thereof. Additionally, the methods and materials can be usedto increase flow velocity of oil in a processing facility, refinery,pre-refinery facility, tubular, reactor, or a combination thereof.Removal of the asphaltene molecules from the substrate by thefunctionalized silicate nanoparticle herein can be used to extractasphaltene deposits that constrict flow in, for example, a tubular, andcan restore flow in a plugged reservoir. Additionally, exfoliation ofasphaltenes can increase permeability in porous media (e.g., a sandscreen that can be deformable such as a polymeric open-cell foam) andflow channels (e.g., a crack in a formation filled with proppant such asobtained in a fracking process). As a result of exfoliation to decreasethe number of asphaltene molecules in an asphaltene particle, oilviscosity also decreases. Lowering the viscosity of the oil improvesproduction efficiency. Additionally, the detrimental effects ofasphaltene can be diminished or eliminated, including alleviation offlocculates of asphaltenes that can plug a reservoir or productiontubing, restrict flow in a transport line, stabilize water-in-oilemulsions, foul a production facility, alter wettability of porous rockin the reservoir, or poison a refinery catalyst.

Thus, in an embodiment, a method for producing decomposed asphalteneincludes disposing a functionalized silicate nanoparticle in an oilenvironment and contacting an asphaltene particle in the oil environmentwith the functionalized silicate nanoparticle. The embodiment alsoincludes decomposing the asphaltene particle to produce decomposedasphaltene. In a certain embodiment, the method also includes breaking awater-in-oil emulsion in response to decomposing the asphalteneparticle. Here the oil-in-water emulsion can be a Pickering emulsionthat is stabilized by asphaltene particles at the water-oil interface.Upon decomposing the asphaltene particles, the emulsion is destabilizedand thus broken.

In addition, water can be introduced by methods such as hot waterinjection, steam stimulation, or a combination comprising at least oneof the foregoing. It is believed that, in this way, the asphalteneparticles decompose as exfoliation of asphaltene molecules in theasphaltene particles occurs. As a result, the viscosity of oil in theoil environment is reduced. Moreover, increasing the mobility of theasphaltene particles by removing them from the substrate is advantageousas noted above. Therefore, the method can be used to enhance oilrecovery. In a further embodiment, the method includes increasing apermeability of a reservoir of the oil environment. According to anotherembodiment, the method further includes producing the oil including thedecomposed or removed asphaltene from the oil environment, whereindecomposing the asphaltene particle occurs prior to producing the oil.Alternatively or in addition, decomposing the asphaltene particle canoccur subsequent to producing the oil.

While one or more embodiments have been shown and described,modifications and substitutions may be made thereto without departingfrom the spirit and scope of the invention. Accordingly, it is to beunderstood that the present invention has been described by way ofillustrations and not limitation. Embodiments herein can be usedindependently or can be combined.

All ranges disclosed herein are inclusive of the endpoints, and theendpoints are independently combinable with each other. The ranges arecontinuous and thus contain every value and subset thereof in the range.The suffix “(s)” as used herein is intended to include both the singularand the plural of the term that it modifies, thereby including at leastone of that term (e.g., the colorant(s) includes at least onecolorants). “Optional” or “optionally” means that the subsequentlydescribed event or circumstance can or cannot occur, and that thedescription includes instances where the event occurs and instanceswhere it does not. As used herein, “combination” is inclusive of blends,mixtures, alloys, reaction products, and the like.

As used herein, “a combination thereof” refers to a combinationcomprising at least one of the named constituents, components,compounds, or elements, optionally together with one or more of the sameclass of constituents, components, compounds, or elements.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. “Or” means “and/or.” It should further be noted that the terms“first,” “second,” and the like herein do not denote any order,quantity, or importance, but rather are used to distinguish one elementfrom another. The modifier “about” used in connection with a quantity isinclusive of the stated value and has the meaning dictated by thecontext (e.g., it includes the degree of error associated withmeasurement of the particular quantity). The conjunction “or” is used tolink objects of a list or alternatives and is not disjunctive; ratherthe elements can be used separately or can be combined together underappropriate circumstances.

What is claimed is:
 1. A composition comprising: a functionalizedsilicate nanoparticle comprising a reaction product of a silicatenanoparticle; and a functionalization compound comprising quaternaryammonium salt, quaternary phosphonium salt, alkoxy silane, halide,guanidine, guanidinium salt, biguanidine, biguanidinium salt, sulfoniumsalt, or a combination thereof; and a fluid, wherein thefunctionalization compound includes a chemical group comprising: a firstportion, the first portion being directly bonded to the silicatenanoparticle in the functionalized silicate nanoparticle; and a secondportion comprising an aromatic moiety or a combination of an aromaticmoiety and a nonaromatic moiety, and the composition is effective toremove an asphaltene particle from a substrate comprising a metal,composite, sand, rock, mineral, glass, formation, downhole element, or acombination thereof, wherein the silicate nanoparticle comprises asilsesquioxane, cyclosilicate, inosilicate, nesosilicate,phyllosilicate, sorosilicate, tectosilicate, or a combination thereof,

wherein the second portion comprises the moiety of formula (4), inwhich, R₁ is an alkyl group, R₂, R₄, and R₅ are each independentlyaromatic groups, and R₃ is a covalent bond or a divalent radicalattached to the first portion.
 2. The composition of claim 1, whereinthe aromatic moiety comprises anthracyl, azulenyl, benzocyclooctenyl,benzocycloheptenyl, biphenylyl, chrysenyl, fluorenyl, indanyl, indenyl,naphthyl, pentalenyl, phenalenyl, phenanthrenyl, phenanthryl, phenyl,pyrenyl, tetrahydronaphthyl, a heteroaryl group, derivatives thereof, ora combination thereof.
 3. A process for removing an asphaltene particlefrom a substrate, the process comprising: contacting the asphalteneparticle with the composition of claim 1, the asphaltene particle beingdisposed on the substrate; interposing the functionalized silicatenanoparticle between the asphaltene particle and the substrate; andseparating the asphaltene particle from the substrate with thefunctionalized silicate nanoparticle to remove the asphaltene particlefrom the substrate.
 4. The process of claim 3, further comprisingexfoliating the asphaltene particle with the functionalized silicatenanoparticle.
 5. The process of claim 4, wherein exfoliating theasphaltene particle comprises intercalating the nonaromatic moiety ofthe functionalized silicate nanoparticle in a gallery of the asphalteneparticle.
 6. The process of claim 4, further comprising heating thefunctionalized silicate nanoparticle to a temperature effective toexfoliate the functionalized silicate nanoparticle, asphaltene particle,or a combination thereof.
 7. The process of claim 3, wherein the fluidcomprises water, oil, carbon dioxide, a liquefied C1-C6 alkane,completion fluid, brine, acid base, or a combination thereof.
 8. Theprocess of claim 3, further comprising contacting the silicatenanoparticle with the functionalization compound in-situ to form thefunctionalized silicate nanoparticle in an environment comprising, apipeline, downhole, formation, tubular, frac feature, production zone,reservoir, or a combination thereof.
 9. The process of claim 3, furthercomprising removing the asphaltene particle from an environment afterseparating the asphaltene particle from the substrate, the environmentcomprising, a pipeline, downhole, formation, tubular, frac feature,production zone, reservoir, or a combination thereof.
 10. The process ofclaim 3, wherein the substrate comprises a metal, composite, sand, rock,mineral, glass, formation, downhole element, or a combination thereof.11. The process of claim 3, wherein the silicate nanoparticle comprisesa silsesquioxane, cyclosilicate, inosilicate, nesosilicate,phyllosilicate, sorosilicate, tectosilicate, or a combination thereof.12. The process of claim 11, wherein the phyllosilicate compriseshalloysite, kaolinite, illite, montmorillonite, vermiculite, talc,palygorskite, pyrophyllite, or a combination thereof.
 13. The process ofclaim 11, wherein the silicate nanoparticle comprises a platelet,sphere, polyhedron, rod, cylinder, or a combination thereof.
 14. Theprocess of claim 3, wherein the first portion of the chemical groupcomprises a bond, linker group, or a combination thereof.
 15. Theprocess of claim 14, wherein the linker group comprises a bond, C1 toC30 alkylene, C3 to C30 cycloalkenylene, C1 to C30 fluoroalkylene, C3 toC30 cycloalkylene, C3 to C30 heterocycloalkylene, C5 to C30 arylene, C6to C40 aralkylene, C6 to C30 aryleneoxy, C2 to C30 heteroarylene, C6 toC40 heteroaralkylene, C2 to C30 alkenylene, C2 to C30 alkynylene, C1 toC30 amide, amine, C1 to C30 oxyalkylene, C1 to C30 oxyarylene, oxygen(O), sulfur (S), or a combination thereof, and the linker group isdisposed between the silicate nanoparticle and the second portion of thechemical group in the functionalized silicate nanoparticle.